Gases

Chapter 5

1
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Elements that exist as gases at 250C and 1 atmosphere

2
3
 Physical Characteristics of
Gases
• Gases assume the volume and shape of their containers.
• Gases are the most compressible state of matter.
• Gases will mix evenly and completely when confined to
the same container.
• Gases have much lower densities than liquids and solids.

4
NO2 gas
 Force
Pressure = Area

(force = mass x
acceleration)

Units of Pressure

1 pascal (Pa) = 1 N/m2

1 atm = 760 mmHg = 760 torr
1 atm = 101,325 Pa

5
10 miles 0.2 atm

4 miles 0.5 atm

Sea level 1 atm

6
Example 5.1

The pressure outside a jet plane flying at high altitude falls

considerably below standard atmospheric pressure. Therefore,
the air inside the cabin must be pressurized to protect the
passengers.

What is the pressure in atmospheres in the cabin if the

barometer reading is 688 mmHg?
Example 5.1

Strategy Because 1 atm = 760 mmHg, the following

conversion factor is needed to obtain the pressure in
atmospheres:

Solution The pressure in the cabin is given by

Example 5.2

The atmospheric pressure in San Francisco on a certain day

was 732 mmHg.

What was the pressure in kPa?

Example 5.2

Strategy
Here we are asked to convert mmHg to kPa.

Because
1 atm = 1.01325 × 105 Pa = 760 mmHg

the conversion factor we need is

Example 5.2

Solution The pressure in kPa is

Manometers Used to Measure Gas Pressures

closed-tube open-tube

12
Apparatus for Studying the Relationship Between
Pressure and Volume of a Gas

13
As P (h) increases V decreases
 Boyle’s Law

P α 1/V
PxV= Constant temperature
Constant amount of gas
P1 xconstant
V1 = P2 x V2 14
Variation in Gas Volume with Temperature at Constant Pressure

As T increases V increases 15
 Variation of Gas Volume with Temperature
at Constant Pressure

Charles’s &
Gay-Lussac’s
Law

VαT Temperature must be

V = constant x in Kelvin
V /T = T
1 1 V /T
2 2
T (K) = t (0C) + 273.15 16
 Avogadro’s Law
V α number of moles (n) Constant temperature
Constant pressure
V = constant x
n
V1 / n1 = V2 / n2

17
 Summary of Gas
Laws
Boyle’s Law

18
Charles’s Law

19
Avogadro’s Law

20
 Ideal Gas Equation
Boyle’s law: P α 1 (at constant n and T)
V
Charles’s law: V α T (at constant n and P)
Avogadro’s law: V α n (at constant P and T)

nT
Vα
P
nT nT
V = constant x = R is the gas constant
R P P

PV = nRT
21
The conditions 0 0C and 1 atm are called standard
temperature and pressure (STP).

Experiments show that at STP, 1 mole of an ideal

gas occupies 22.414 L.

PV = nRT
PV (1 atm)(22.414L)
R= =
nT (1 mol)(273.15 K)

R = 0.082057 L • atm / (mol • K)

22
Example 5.3

Sulfur hexafluoride (SF6) is a

colorless and odorless gas.

Due to its lack of chemical

reactivity, it is used as an
insulator in electronic
equipment.

Calculate the pressure (in atm)

exerted by 1.82 moles of the
gas in a steel vessel of volume
5.43 L at 69.5°C.
Example 5.3

Strategy
The problem gives the amount of the gas and its volume and
temperature.

Is the gas undergoing a change in any of its properties?

What equation should we use to solve for the pressure?

What temperature unit should we use?

Example 5.3

Solution Because no changes in gas properties occur, we can

use the ideal gas equation to calculate the pressure.

Rearranging Equation (5.8), we write

Example 5.4

Calculate the volume (in L) occupied by 7.40 g of NH3 at STP.

Example 5.4

Strategy
What is the volume of one mole of an ideal gas at STP?

How many moles are there in 7.40 g of NH3?

Solution
Recognizing that 1 mole of an ideal gas occupies 22.41 L at
STP and using the molar mass of NH3 (17.03 g), we write the
sequence of conversions as
Example 5.4
So the volume of NH3 is given by

It is often true in chemistry, particularly in gas-law calculations,

that a problem can be solved in more than one way. Here the
problem can also be solved by first converting 7.40 g of NH3 to
number of moles of NH3, and then applying the ideal gas
equation (V = nRT/P). Try it.

Check Because 7.40 g of NH3 is smaller than its molar mass,

its volume at STP should be smaller than 22.41 L. Therefore,
the answer is reasonable.
Example 5.5

An inflated helium balloon with a

volume of 0.55 L at sea level
(1.0 atm) is allowed to rise to a
height of 6.5 km, where the
pressure is about 0.40 atm.

Assuming that the temperature

remains constant, what is the
final volume of the balloon?

A scientific research
helium balloon.
Example 5.5

Strategy The amount of gas inside the balloon and its

temperature remain constant, but both the pressure and the
volume change. What gas law do you need?

Solution We start with Equation (5.9)

Because n1 = n2 and T1 = T2,

which is Boyle’s law [see Equation (5.2)].

Example 5.5
The given information is tabulated:
Initial Conditions Final Conditions
P1 = 1.0 atm P2 = 0.40 atm
V1 = 0.55 L V2 = ?

Therefore,

Check When pressure applied on the balloon is reduced (at

constant temperature), the helium gas expands and the
balloon’s volume increases. The final volume is greater than
the initial volume, so the answer is reasonable.
Example 5.6

Argon is an inert gas used in

lightbulbs to retard the
vaporization of the tungsten
filament.

A certain lightbulb containing

argon at 1.20 atm and 18°C is
heated to 85°C at constant
volume.

Calculate its final pressure

(in atm).
Electric lightbulbs are
usually filled with
argon.
Example 5.6
Strategy The temperature and pressure of argon change but
the amount and volume of gas remain the same.

What equation would you use to solve for the final pressure?

What temperature unit should you use?

Solution Because n1 = n2 and V1 = V2, Equation (5.9) becomes

which is Charles’s law [see Equation (5.6)].

Example 5.6
Next we write
Initial Conditions Final Conditions
P1 = 1.20 atm P2 = ?
T1 = (18 + 273) K = 291 K T2 = (85 + 273) K = 358 K

The final pressure is given by

Check At constant volume, the pressure of a given amount of

gas is directly proportional to its absolute temperature.
Therefore the increase in pressure is reasonable.
Example 5.7

A small bubble rises from the bottom of a lake, where the

temperature and pressure are 8°C and 6.4 atm, to the water’s
surface, where the temperature is 25°C and the pressure
is 1.0 atm.

Calculate the final volume (in mL) of the bubble if its initial
volume was 2.1 mL.
Example 5.7

Strategy In solving this kind of problem, where a lot of

information is given, it is sometimes helpful to make a sketch of
the situation, as shown here:

What temperature unit should be used in the calculation?

Example 5.7
Solution According to Equation (5.9)

We assume that the amount of air in the bubble remains

constant, that is, n1 = n2 so that

which is Equation (5.10).

Example 5.7

The given information is summarized:

Initial Conditions Final Conditions

P1 = 6.4 atm P2 = 1.0 atm
V1 = 2.1 mL V2 = ?
T1 = (8 + 273) K = 281 K T2 = (25 + 273) K = 298 K

Rearranging Equation (5.10) gives

Example 5.7

Check We see that the final volume involves multiplying the

initial volume by a ratio of pressures (P1/P2) and a ratio of
temperatures (T2/T1).

Recall that volume is inversely proportional to pressure, and

volume is directly proportional to temperature.

Because the pressure decreases and temperature increases as

the bubble rises, we expect the bubble’s volume to increase.

In fact, here the change in pressure plays a greater role in the

volume change.
Density (d) Calculations

m PM m is the mass of the gas in

d= = g
V RT M is the molar mass of the gas

Molar Mass (M ) of a Gaseous Substance

dRT
M= d is the density of the gas in
P
g/L

40
Example 5.8

Calculate the density of carbon dioxide (CO2) in grams per liter

(g/L) at 0.990 atm and 55°C.
Example 5.8

Strategy We need Equation (5.11) to calculate gas density.

Is sufficient information provided in the problem?

What temperature unit should be used?

Solution To use Equation (5.11), we convert temperature to

kelvins (T = 273 + 55 = 328 K) and use 44.01 g for the molar
mass of CO2:
Example 5.8

Alternatively, we can solve for the density by writing

Assuming that we have 1 mole of CO2, the mass is 44.01 g.

The volume of the gas can be obtained from the ideal gas
equation
Example 5.8

Therefore, the density of CO2 is given by

Comment ln units of grams per milliliter, the gas density is

1.62 × 10−3 g/mL, which is a very small number. In comparison,
the density of water is 1.0 g/mL and that of gold is 19.3 g/cm3.
Example 5.9

A chemist has synthesized a greenish-yellow gaseous

compound of chlorine and oxygen and finds that its density is
7.71 g/L at 36°C and 2.88 atm.

Calculate the molar mass of the compound and determine its

molecular formula.
Example 5.9

Strategy
Because Equations (5.11) and (5.12) are rearrangements of
each other, we can calculate the molar mass of a gas if we
know its density, temperature, and pressure.

The molecular formula of the compound must be consistent

with its molar mass. What temperature unit should we use?
Example 5.9
Solution From Equation (5.12)

Alternatively, we can solve for the molar mass by writing

From the given density we know there are 7.71 g of the

gas in 1 L.
Example 5.9

The number of moles of the gas in this volume can be obtained

from the ideal gas equation

Therefore, the molar mass is given by

Example 5.9

We can determine the molecular formula of the compound by

trial and error, using only the knowledge of the molar masses of
chlorine (35.45 g) and oxygen (16.00 g).

We know that a compound containing one Cl atom and one O

atom would have a molar mass of 51.45 g, which is too low,
while the molar mass of a compound made up of two Cl atoms
and one O atom is 86.90 g, which is too high.

Thus, the compound must contain one Cl atom and two O

atoms and have the formula ClO2, which has a molar mass of
67.45 g.
Example 5.10

Chemical analysis of a gaseous compound showed that it

contained 33.0 percent silicon (Si) and 67.0 percent fluorine (F)
by mass.

At 35°C, 0.210 L of the compound exerted a pressure of 1.70

atm.

If the mass of 0.210 L of the compound was 2.38 g, calculate

the molecular formula of the compound.
Example 5.10

Strategy This problem can be divided into two parts.

First, it asks for the empirical formula of the compound from the
percent by mass of Si and F.

Second, the information provided enables us to calculate the

molar mass of the compound and hence determine its
molecular formula.

What is the relationship between empirical molar mass and

molar mass calculated from the molecular formula?
Example 5.10

Solution We follow the procedure in Example 3.9 (p. 86) to

calculate the empirical formula by assuming that we have 100 g
of the compound, so the percentages are converted to grams.

The number of moles of Si and F are given by

Therefore, the empirical formula is Si1.17F3.53, or, dividing by the

smaller subscript (1.17), we obtain SiF3.
Example 5.10

To calculate the molar mass of the compound, we need first to

calculate the number of moles contained in 2.38 g of the
compound. From the ideal gas equation

Because there are 2.38 g in 0.0141 mole of the compound, the

mass in 1 mole, or the molar mass, is given by
Example 5.10
The molar mass of the empirical formula SiF3 is 85.09 g.

Recall that the ratio (molar mass/empirical molar mass) is

always an integer (169/85.09 ≈ 2).

Therefore, the molecular formula of the compound must be

(SiF3)2 or Si2F6 .
 Gas
Stoichiometry

55
Example 5.11

Calculate the volume of O2 (in liters)

required for the complete combustion
of 7.64 L of acetylene (C2H2)
measured at the same temperature
and pressure.

The reaction of calcium

carbide (CaC2) with water
produces acetylene (C2H2),
a flammable gas.
Example 5.11

Strategy Note that the temperature and pressure of O2 and

C2H2 are the same. Which gas law do we need to relate the
volume of the gases to the moles of gases?

Solution According to Avogadro’s law, at the same

temperature and pressure, the number of moles of gases are
directly related to their volumes. From the equation, we
have 5 mol O2 2 mol C2H2; therefore, we can also write 5
L O2 2 L C2H2. The volume of O2 that will react with 7.64 L
C2H2 is given by
Example 5.12
Sodium azide (NaN3) is used in some
automobile air bags. The impact of a
collision triggers the decomposition of
NaN3 as follows:

The nitrogen gas produced quickly

inflates the bag between the driver
and the windshield and dashboard.

Calculate the volume of N2 generated

at 80°C and 823 mmHg by the An air bag can
decomposition of 60.0 g of NaN3. protect the driver in
an automobile
collision.
Example 5.12

Strategy From the balanced equation we see that

2 mol NaN3 3 mol N2 so the conversion factor between NaN3
and N2 is

Because the mass of NaN3 is given, we can calculate the

number of moles of NaN3 and hence the number of moles of N2
produced.

Finally, we can calculate the volume of N2 using the ideal gas

equation.
Example 5.12

Solution First we calculate number of moles of N2 produced by

60.0 g NaN3 using the following sequence of conversions

so that

The volume of 1.38 moles of N2 can be obtained by using the

ideal gas equation:
Example 5.13

Aqueous lithium hydroxide solution is used to purify air in

spacecrafts and submarines because it absorbs carbon dioxide,
which is an end product of metabolism, according to the
equation

The pressure of carbon dioxide inside the cabin of a submarine

having a volume of 2.4 × 105 L is 7.9 × 10−3 atm at 312 K. A
solution of lithium hydroxide (LiOH) of negligible volume is
introduced into the cabin. Eventually the pressure of CO2 falls
to 1.2 × 10−4 atm. How many grams of lithium carbonate are
formed by this process?
Example 5.13
Strategy How do we calculate the number of moles of CO2
reacted from the drop in CO2 pressure?

From the ideal gas equation we write

At constant T and V, the change in pressure of CO2, ΔP,

corresponds to the change in the number of moles of CO2, Δn.
Thus,

What is the conversion factor between CO2 and Li2CO3?

Example 5.13
Solution The drop in CO2 pressure is

(7.9 × 10−3 atm) − (1.2 × 10−4 atm) or 7.8 × 10−3 atm

Therefore, the number of moles of CO2 reacted is given by

From the chemical equation we see that

1 mol CO2 1 mol Li2CO3

so the amount of Li2CO3 formed is also 73 moles.

Example 5.13

Then, with the molar mass of Li2CO3 (73.89 g), we calculate its
mass:
 Dalton’s Law of Partial Pressures
V and T are constant

P1 P2 Ptotal = P1 + P2
65
Consider a case in which two gases, A and B, are in a
container of volume V.

nART
PA = nA is the number of moles of A
V
nBRT nB is the number of moles of B
PB =
V
nA nB
PT = PA + PB XA = XB =
nA + nB n A + nB

PA = XA PT PB = XB PT

ni
Pi = Xi PT mole fraction (Xi ) =
nT
66
Example 5.14

A mixture of gases contains 4.46 moles of neon (Ne), 0.74 mole

of argon (Ar), and 2.15 moles of xenon (Xe).

Calculate the partial pressures of the gases if the total pressure

is 2.00 atm at a certain temperature.
Example 5.14

Strategy What is the relationship between the partial pressure

of a gas and the total gas pressure?

How do we calculate the mole fraction of a gas?

Solution According to Equation (5.14), the partial pressure of

Ne (PNe) is equal to the product of its mole fraction (XNe) and the
total pressure (PT)
Example 5.14

Using Equation (5.13), we calculate the mole fraction of Ne as

follows:

Therefore,
Example 5.14
Similarly,

and

Check Make sure that the sum of the partial pressures is equal
to the given total pressure; that is,

(1.21 + 0.20 + 0.586) atm = 2.00 atm.

Collecting a Gas over Water

2KClO3 (s) 2KCl (s) + 3O2 (g)

71
PT = PO2 + PH 2O
Vapor of Water and Temperature

72
Example 5.15

Oxygen gas generated by the decomposition of potassium

chlorate is collected as shown in Figure 5.15.

The volume of oxygen collected at 24°C and atmospheric

pressure of 762 mmHg is 128 mL.

Calculate the mass (in grams) of oxygen gas obtained.

The pressure of the water vapor at 24°C is 22.4 mmHg.

Example 5.15

Strategy To solve for the mass of O2 generated, we must first

calculate the partial pressure of O2 in the mixture.

What gas law do we need?

How do we convert pressure of O2 gas to mass of O2 in grams?

Solution From Dalton’s law of partial pressures we know that

Example 5.15

Therefore,

From the ideal gas equation we write

where m and are the mass of O2 collected and the molar

mass of O2, respectively.
Example 5.15

Rearranging the equation we obtain

Check The density of the oxygen gas is (0.164 g/0.128 L), or

1.28 g/L, which is a reasonable value for gases under
atmospheric conditions (see Example 5.8).
 Chemistry in Action:
Scuba Diving and the Gas Laws
Depth (ft) Pressure
(atm)
0 1

33 2

66 3

P V

77
 Kinetic Molecular Theory of Gases
1. A gas is composed of molecules that are separated from
each other by distances far greater than their own
dimensions. The molecules can be considered to be points;
that is, they possess mass but have negligible volume.
2. Gas molecules are in constant motion in random directions,
and they frequently collide with one another. Collisions
among molecules are perfectly elastic.
3. Gas molecules exert neither attractive nor repulsive forces
on one another.
4. The average kinetic energy of the molecules is proportional
to the temperature of the gas in kelvins. Any two gases at
the same temperature will have the same average kinetic
energy
KE = ½ mu2
78
 Kinetic theory of gases and
…
• Compressibility of Gases
• Boyle’s Law
P α collision rate with wall
Collision rate α number density
Number density α 1/V
P α 1/V
• Charles’s Law
P α collision rate with wall
Collision rate α average kinetic energy of gas molecules
Average kinetic energy α T
PαT

79
 Kinetic theory of gases and
…
• Avogadro’s Law
P α collision rate with wall
Collision rate α number density
Number density α n
Pαn
• Dalton’s Law of Partial Pressures
Molecules do not attract or repel one another
P exerted by one type of molecule is unaffected by the
presence of another gas
Ptotal = ΣPi

80
Apparatus for Studying Molecular Speed Distribution

81
 The distribution of speeds
of three different gases
at the same temperature

The distribution of speeds

for nitrogen gas molecules
at three different temperatures

urms = √ 3RT
M
82
Example 5.16

Calculate the root-mean-square speeds of helium atoms and

nitrogen molecules in m/s at 25°C.
Example 5.16

Strategy To calculate the root-mean-square speed we need

Equation (5.16).

What units should we use for R and so that urms will be

expressed in m/s?

Solution
To calculate urms, the units of R should be 8.314 J/K · mol and,
because 1 J = 1 kg m2/s2, the molar mass must be in kg/mol.

The molar mass of He is 4.003 g/mol, or 4.003 × 10−3 kg/mol.

Example 5.16

From Equation (5.16),

Using the conversion factor 1 J = 1 kg m2/s2 we get

Example 5.16
The procedure is the same for N2, the molar mass of which is
28.02 g/mol, or 2.802 × 10−2 kg/mol so that we write

Check
Because He is a lighter gas, we expect it to move faster, on
average, than N2. A quick way to check the answers is to note
that the ratio of the two urms values (1.36 × 103/515 ≈ 2.6) should
be equal to the square root of the ratios of the molar masses of
N2 to He, that is, .
 Chemistry in Action: Super Cold Atoms

Maxwell velocity distribution of Rb atoms at about 1.7 x 10−7 K

87
Bose-Einstein condensate (BEC)
Gas diffusion is the gradual mixing of molecules of one gas
with molecules of another by virtue of their kinetic properties.

√
r1 M2
=
r2 M1

molecular path
NH4Cl

NH3 HCl
17 g/mol 36 g/mol
88
Gas effusion is the process by which gas under pressure
escapes from one compartment of a container to another by
passing through a small opening.

√
r1 t2 M2
= =
r2 t1 M1

89
Example 5.17
A flammable gas made up only of
carbon and hydrogen is found to
effuse through a porous barrier in
1.50 min.

Under the same conditions of

temperature and pressure, it
takes an equal volume of bromine
vapor 4.73 min to effuse through
the same barrier.
Calculate the molar mass of the
unknown gas, and suggest what
this gas might be.
Gas effusion. Gas
molecules move from a
high-pressure
region (left) to a low-
pressure
one through a pinhole.
Example 5.17

Strategy The rate of diffusion is the number of molecules

passing through a porous barrier in a given time.

The longer the time it takes, the slower is the rate.

Therefore, the rate is inversely proportional to the time required

for diffusion.

Equation (5.17) can now be written as r1/r2 = t2/t1 = ,

where t1 and t2 are the times for effusion for gases 1 and 2,
respectively.
Example 5.17
Solution From the molar mass of Br2, we write

Where is the molar mass of the unknown gas. Solving for

we obtain

Because the molar mass of carbon is 12.01 g and that of

hydrogen is 1.008 g, the gas is methane (CH4).
 Deviations from Ideal Behavior

1 mole of ideal gas

Repulsive Forces
PV = nRT
PV = 1.0
n=
RT
Attractive Forces

93
Effect of intermolecular forces on the pressure exerted by a gas.

94
Van der Waals equation
nonideal gas

an 2
( P + V2 ) (V – nb) = nRT
}
}

correcte correcte
d d
pressure volume

95
Example 5.18

Given that 3.50 moles of NH3 occupy 5.20 L at 47°C, calculate

the pressure of the gas (in atm) using

(a)the ideal gas equation and

(b)the van der Waals equation.

Example 5.18

Strategy
To calculate the pressure of NH3 using the ideal gas equation,
we proceed as in Example 5.3.

What corrections are made to the pressure and volume terms in

the van der Waals equation?
Example 5.18

Solution
(a)We have the following data:
V = 5.20 L
T = (47 + 273) K = 320 K
n = 3.50 mol
R = 0.0821 L · atm/K · mol
Substituting these values in the ideal gas equation, we write
Example 5.18
(b) We need Equation (5.18). It is convenient to first calculate
the correction terms in Equation (5.18) separately. From
Table 5.4, we have

a = 4.17 atm · L2/mol2

b = 0.0371 L/mol

so that the correction terms for pressure and volume are

Example 5.18
Finally, substituting these values in the van der Waals equation,
we have

Check Based on your understanding of nonideal gas behavior,

is it reasonable that the pressure calculated using the van der
Waals equation should be smaller than that using the ideal gas
equation? Why?